The present invention relates to monomers which are useful in the production of polymers, and in particular to network polymers, to the polymers obtained therefrom and to methods of producing these polymers, in particular using radiation curing, for example ultraviolet or thermal radiation.
Many polymers such as polyethylenes, polystyrenes, polyvinylidene fluorides, polytetrafluoroethylenes (e.g. teflon(trademark)), nylons, polyesters etc. are used every day in a wide variety of purposes from plastic wrap and plastic cups to sensors and non-stick surfaces to yield high strength materials.
WO 98/29107 describes certain polydiallyamine-based bile acid sequestrants, which are formed by polymerisation of the monomer in solution.
The applicants have found that certain compounds with two or more multiple bonds may be activated by the presence of an electron withdrawing group, in particular where the electron withdrawing group is at a position which is alpha or beta to one or both of the double bonds to make them polymerisable, for example under the influence of radiation or an electron beam, or in the presence of a chemical initiator. Polymeric compounds obtained therefrom include cyclic rings. These have many advantageous properties. In particular, the invention can be used to generate products such as network polymers or conducting polymers depending upon the other aspects of the structure of the compounds.
Certain monomers are new and these form a further aspect of the invention. In particular, the invention provides a compound of formula (I) 
where R1 is CH and R6 is a bond, or R1 and R6 together form an electron withdrawing group;
R2 and R3 are independently selected from (CR7R8)n, or a group CR9R10, xe2x80x94(CR7R8CR9R10)xe2x80x94 or xe2x80x94(CR9R10CR7R8)xe2x80x94 where n is 0, 1, or 2, R7 and R8 are independently selected from hydrogen or alkyl, and either one of R9 or R10 is hydrogen and the other is an electron withdrawing group, or R9 and R10 together form an electron withdrawing group, and
R4 and R5 are independently selected from CH or CR11 where R11 is an electron withdrawing group;
the dotted lines indicate the presence or absence of a bond, and X1 is a group CX2X3 where the dotted line bond to which it is attached is absent and a group CX2 where the dotted line bond to which it is attached is present, Y1 is a group CY2Y3 where the dotted line bond to which it is attached is absent and a group CY2 where the dotted line bond to which it is attached is present, and X2, X3, Y2 and Y3 are independently selected from hydrogen and fluorine;
R16 is a bridging group of valency r and r is an integer of 2 or more, subject to the following provisos:
(i) that at least one of (a) R1 and R6 or (b) R2 and R3 or (c) R4 and R5 includes an electron withdrawing group.
Preferably the compounds of formula (I) are of formula (IA) 
where R1, R2, R3, R4, R5, R6, R16, X2, X3, Y2 and Y3 are as defined in relation to formula (I).
Suitably the compounds of formula (IA) are subject to the further proviso:
(ii) that where R16 is a group xe2x80x94(CH2)10xe2x80x94, R2 and R3 are CH2 groups, R4 and R5 are CH groups and X1, X2, X3 and X4 hydrogen, R1 is other than a group N+CH3Brxe2x88x92 where R6 is a bond.
Suitably, where R16 is a alkylene group, R2 and R3 are CH2 groups, R4 and R5 are CH groups, X1, X2, X3 and X4 hydrogen, R1 is other than a group N+R12 (Zmxe2x88x92)1/m as hereinafter defined, where R6 is a bond.
Preferably, where R2 and R3 are both (CR7R8)n, at least one n is 1 or 2. Suitably in formula (I), n is 1 or 2.
On polymerisation of these compounds, networks are formed whose properties may be selected depending upon the precise nature of the R16 group, the amount of diluent, plasticiser or chain terminator present and the polymerisation conditions employed. Polymerisation will occur in accordance with the general scheme set out in FIG. 1 hereinafter.
When the dotted bonds in sub formula (I) are present, the resulting polymer will comprise polyacetylene chains. This can lead to a conjugated system and consequently a conducting polymer.
Suitably the compound is designed such that it cyclopolymerises under the influence of ultraviolet or thermal radiation, preferably. ultraviolet radiation. Cyclopolymerisation may take place either spontaneously in the presence of the appropriate radiation or in the presence of a suitable initiator, for example 2,2xe2x80x2-azobisisobutyronitrile (AIBN), aromatic ketones such as benzophenones in particular acetophenone; chlorinated acetophenones such as di- or tri-chloroacetophenone; dialkoxyacetophenones such as dimethoxyacetophenones (sold under the Trade name xe2x80x9cIrgacure 651xe2x80x9d); dialkylhydroxyacetophenones such as dimethylhydroxyacetophenone (sold under the Trade name xe2x80x9cDarocure 1173xe2x80x9d); substituted dialkylhydroxyacetophenone alkyl ethers such compounds of formula 
where Ry is alkyl and in particular 2,2-dimethylethyl, Rx is hydroxy or halogen such as chloro, and Rp and Rq are independently selected from alkyl or halogen such as chloro (examples of which are sold under the Trade names xe2x80x9cDarocure 1116xe2x80x9d and xe2x80x9cTrigonal P1xe2x80x9d); 1-benzoylcyclohexanol-2 (sold under the Trade name xe2x80x9cIrgacure 184xe2x80x9d); benzoin or derivatives such as benzoin acetate, benzoin alkyl ethers in particular benzoin butyl ether, dialkoxybenzoins such as dimethoxybenzoin or deoxybenzoin; dibenzyl ketone; acyloxime esters such as methyl or ethyl esters of acyloxime (sold under the trade name xe2x80x9cQuantaqure PDOxe2x80x9d); acylphosphine oxides, acylphosphonates such as dialkylacylphosphonate, ketosulphides for example of formula 
where Rz is alkyl and Ar is an aryl group; dibenzoyl disulphides such as 4,4xe2x80x2-dialkylbenzoyldisulphide; diphenyldithiocarbonate; benzophenone; 4,4xe2x80x2-bis(N,N-dialkylamino)benzophenone; fluorenone; thioxanthone; benzil; or a compound of formula 
where Ar is an aryl group such as phenyl and Rz is alkyl such as methyl (sold under the trade name xe2x80x9cSpeedcure BMDSxe2x80x9d). The compound may be polymerised under the influence of a free radical or ion initiator as is understood in the art, as well as by application of an electron beam.
As used herein, the term xe2x80x9calkylxe2x80x9d refers to straight or branched chain alkyl groups, suitably containing up, to 20 and preferably up to 6 carbon atoms. The terms xe2x80x9calkenylxe2x80x9d and xe2x80x9calkynylxe2x80x9d refer to unsaturated straight of branched chains which include for example from 2-20 carbon atoms, for example from 2 to 6 carbon atoms. Chains may include one or more double or triple bonds respectively. In addition, the term xe2x80x9carylxe2x80x9d refers to aromatic groups such as phenyl or naphthyl.
The term xe2x80x9chydrocarbylxe2x80x9d refers to any structure comprising carbon and hydrogen atoms. For example, these may be alkyl, alkenyl, alkynyl, aryl such as phenyl or napthyl, aralkyl, cycloalkyl, cycloalkenyl or cycloalkynyl. Suitably they will contain up to 20 and preferably up to 10 carbon atoms. The term xe2x80x9cheterocyclylxe2x80x9d includes aromatic or non-aromatic rings, for example containing from 4 to 20, suitably from 5 to 10 ring atoms, at least one of which is a heteroatom such as oxygen, sulphur or nitrogen. Examples of such groups include furyl, thienyl, pyrrolyl, pyrrolidinyl, imidazolyl, triazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, iosquinolinyl, quinoxalinyl, benzthiazolyl, benzoxazolyl, benzothienyl or benzofuryl.
The term xe2x80x9cfunctional groupxe2x80x9d refers to reactive groups such as halo, cyano, nitro, oxo, C(O)nRa, ORa, S(O)tRa, NRbRc, OC(O)NRbRc, C(O)NRbRc, OC(O)NRbRc, xe2x80x94NR7C(CO)nR6, xe2x80x94NRaCONRbRc, xe2x80x94Cxe2x95x90NORa, xe2x80x94Nxe2x95x90CRbRc, S(O)tNRbRc, C(S)nRa, C(S)ORa, C(S)NRbRc or xe2x80x94NRbS(O)tRa where Ra, Rb and Rc are independently selected from hydrogen or optionally substituted hydrocarbyl, or Rb and Rc together form an optionally substituted ring which optionally contains further heteroatoms such as S(O)s, oxygen and nitrogen, n is an integer of 1 or 2, t is 0 or an integer of 1-3. In particular the functional groups are groups such as halo, cyano, nitro, oxo, C(O)nRa, ORa, S(O)tRa, NRbRc, OC(O)NRbRc, C(O)NRbRc, OC(O)NRbRc, xe2x80x94NR7C(O)nR6, xe2x80x94NRaCONRbRc, xe2x80x94NRaCSNRbRc, xe2x80x94Cxe2x95x90NORa, xe2x80x94Nxe2x95x90CRbRc, S(O)tNRbRc, or xe2x80x94NRbS(O)tRa where Ra, Rb and Rc, n and t are as defined above.
The term xe2x80x9cheteroatomxe2x80x9d as used herein refers to non-carbon atoms such as oxygen, nitrogen or sulphur atoms. Where the nitrogen atoms are present, they will generally be present as part of an amino residue so that they will be substituted for example by hydrogen or alkyl.
The term xe2x80x9camidexe2x80x9d is generally understood to refer to a group of formula C(O)NRaRb where Ra and Rb are hydrogen or an optionally substituted hydrocarbyl group. The term xe2x80x9csulphonamidexe2x80x9d correspondingly relates to groups of formula S(O)2NRaRb.
The nature of the electron withdrawing group or groups used in any particular compound of formula (I) will depend upon its position in relation to the double bond it is required to activate, as well as the nature of any other functional groups within the compound.
In a preferred embodiment, R1 and R6 form an electron withdrawing group. For example, R1 is a heteroatom or a substituted heteroatom which has electron withdrawing properties, for example a group N+R12(Zmxe2x88x92)1/m, S(O)pR13, B, P(O)qR14 or Si(R15) where R12, R13, R14 and R15 are independently selected from hydrogen or hydrocarbyl, Z is a anion of valency m, p is 0, 1 or 2, and q is 0, 1, 2 or 3; and R6 is a bond. Alternatively, R1 is a group CH and R6 is a group xe2x80x94C(O)Oxe2x80x94, xe2x80x94OC(O)xe2x80x94 or S(O)2, suitably C(O)Oxe2x80x94, or xe2x80x94OC(O)xe2x80x94 and preferably S(O)2. In yet a further alternative, R1 and R6 form an amide or sulphonamide group where R1 is nitrogen and R6 is C(O) or S(O)2.
Most preferably, R1 is a group N+R12(Zmxe2x88x92)1/m, S(O)pR13, B, P(O)qR14 or Si(R15) where R12, R13, R14 and R15 are independently selected from hydrogen or alkyl in particular C1-3 alkyl, Z is a halogen. In particular R1 is a group N+R12(Zmxe2x88x92)1/m, and R6 is a bond. The nature of the anion Z will affect the physical properties of the final polymer such as its porosity, water retention and in particular, its conductivity. Suitable anions for the Z group include halide ions such as fluoride, chloride, bromide or iodide, borides such as boron tetrafluoride; carboxylic acid esters such as those of formula R14C(O)Oxe2x88x92 where R14 is an optionally substituted hydrocarbyl group group such as haloalkyl, in particular trifluoromethyl; and other anionic groups such as mesylate and tosylate. In general, the water permeability of the ultimate polymer will vary as follows:
PF6xe2x88x92 less than BF4xe2x88x92 less than CF3SO3xe2x88x92 less than CF3COOxe2x88x92 less than NO3xe2x88x92 less than SO42xe2x88x92 less than Ixe2x88x92 less than Brxe2x88x92 less than Clxe2x88x92
Other factors which affect the water permeability of the polymer is the nature of the bridging group. When this contains for example perhaloalkyl substituents such as perfluoroalkyl, it will be largely water impermeable as compared to polymers which have alkylene bridging groups optionally interposed with say oxygen.
In a particular embodiment, the combination of R1 and R6 forms an amide group or sulphonamide group, where R1 is a nitrogen atom and R6 is a carbonyl group or sulphonyl group.
Alternatively, where the activation is effected by electron withdrawing groups at a position indicated by R2 or R3, suitable electron withdrawing groups R9 and R10 include COCH2CN and COCH3 preferably R9 and R10 together form an oxo group.
Where R11 is an electron withdrawing group, it is suitably COCH3. Preferably, X2, X3, Y2 and Y3 are all hydrogen.
Suitably r is an integer of from 2 to 6, preferably from 2 to 4. The polymers produced can be useful in a number of different applications including the production of network polymers and those used in thermal management.
Thermal management is the control of optical properties of materials across solar and thermal wavebands (xcx9c0.7-12 microns). This control of transmitted, reflected and absorbed radiation gives the potential to design systems that can selectively perform different tasks at different wavelengths. For example use of silver coatings by the glazing industry to limit solar transmission (material transparent at visible wavelengths but reflective across the solar) and thus prevent xe2x80x98greenhousexe2x80x99 heating. Other example could be solar water heaters where the material is transparent at NIR wavelengths but reflective at longer wavelengths. Benefits of thermal management could be in reduced air conditioning/heating costs.
The properties of the polymer obtained in accordance with the invention will depend upon a variety of factors but will depend very largely on the nature of the group R16.
Suitably R16 will comprise a bridging group for example as is known in polymer, paint or coating chemistry. These may include straight or branched chain alkyl groups, optionally substituted or interposed with functional groups or siloxane groups such as alkyl siloxanes. Suitable bridging groups include those found in polyethylenes, polypropylenes, nylons, as listed in Table 1.
The length of the bridging group will affect the properties of the polymeric material derived from this. This can be used to design polymers with properties which are best suited to the application. For instance when the bridging group comprises relatively long chains, (for example with in excess of 6 repeat units, for example from 6-20 repeat units), the polymer will have pliable plastic properties. Alternatively, when the bridging group is relatively short, (e.g. less than 6 repeat units) the material will be more brittle.
Other possibility for producing particular properties arises from the possibility of producing copolymers where another monomeric compound, for example one which is not of formula (I), is mixed with the compound of formula (I) prior to polymerisation. Such monomers are known in the art. They include diallyamine compounds as well as others conventionally used.
Composites may also be produced by polymerising compounds of formula (I) in the presence of other moieties such as graphite, ethers such-as crown ethers or thioethers, thalocyanines, bipyridyls or liquid crystal compounds, all of which will produce composite polymers with modified properties.
Examples of possible bridging groups R16 where r is 2 are groups of sub-formula (II)
xe2x80x94Z1xe2x80x94(Q1)axe2x80x94(Z2xe2x80x94Q2)bxe2x80x94Z3xe2x80x94xe2x80x83xe2x80x83(II)
where a and b are independently selected from 0, 1 or 2, Z1, Z2 and Z3 are independently selected from a bond, an optionally substituted linear or branched alkyl or alkene chain wherein optionally one or more non-adjacent carbon atoms is replaced with a heteroatom or an amide group, Q1 and Q2 are independently selected from an optionally substituted carbocyclic or heterocyclic ring which optionally contains bridging alkyl groups;
a and b are independently selected from 0, 1 or 2.
Suitable carbocyclic rings for Q1 and Q2 include cycloalkyl groups for example of from 1 to 20 carbon atoms. Bridged carbocyclic ring structures include 1,4-bicyclo[2.2.2]octane, decalin, bicyclo[2.2.1]heptane, cubane, diadamantane, adamantane. Suitable heterocyclic rings include any of the above where one or more non adjacent carbon atoms are replaced by a heteroatom such as oxygen, sulphur or nitrogen (including amino or substituted amino), or a caboxyl or an amide group. Suitable optional substitutents for the groups Q1 and Q2include one or more groups selected from alkyl, alkenyl, alkynyl, aryl, aralkyl such as benzyl, or functional groups as defined above. Particularly substitutents for the groups Q1 and Q2are oxo and halogen in particular fluorine and chlorine.
Suitable optional substituents for the alkyl and alkene groups Z1, Z2 and Z3 include aryl, aralkyl and functional groups as defined above. Particular substituents include halogens such as fluorine and chlorine, and oxo.
Other sorts of bridging groups R16 include electrically conducting chains, for instance, electrically conducting unsaturated chains such as alkenes or chains incorporating aromatic or heterocyclic rings. For instance, the group R16 in a compound of formula (I) may comprise a di substituted conducting unit such as a tertathiafulvalene. Thus an example of a compound of formula (I) is a compound of formula (III 
where R21 and R23 are each groups of sub-formula (IV) 
where X2, X3, Y2, Y3, R1, R2, R3, R4, R5 and R6 are as defined in relation to formula (I) above and R1 and R19 are independently selected from groups of sub-formula (II) as given above, q is an integer of 1 or more, for example from 1 to 6, and Q is sulphur or NH. In particular R17, R18, R19 and R20 are alkyl groups.
Polymerisation of compounds of formula (III) will give cross-linked networks where the cross-linking occurs through the diene units. This will lead to a very stable material with robust physical properties. Once again, varying the length of the spacer groups R17, R18, R19 and R20 will lead to materials with designer properties. For instance when R17, R18, R19 and R20 are relatively long chains, the polymer will have pliable plastic properties. Alternatively, when the chains R17, R18, R19 and R20 are relatively short, the material will be more brittle.
Where R1 and R6 together form a group xe2x80x94N+R7Zxe2x88x92, varying the counter ion Zxe2x88x92 can also be used to adjust the physical properties of the polymer, such as water retention, porosity or conductivity. The materials will exhibit conducting properties, making them suitable as organic semiconductors for example for use as interconnects for IC chips etc.
Alternatively, a bridging group R16 may comprise a tetra or octa substituted non-linear optic unit such as an optionally substituted porphyrin or phthalocyanine. Suitable optional substitutents in addition to the groups of sub-formula (I) are hydrocarbyl groups such as alkyl in particular methyl. An example of such a compound is a compound of formula (VI) 
where R17, R18, R19, R20, R21, R22, R23 and R24 are as defined in relation to formula (III) above and R25, R26, R27 and R28 are each independently selected from hydrogen or hydrocarbyl groups such as alkyl and in particular methyl; and the compound optionally contains a metal ion within the macrocyclic heterocyclic unit. An alternative compound is a compound of formula (VIA) 
where R50 through to R65 are independently selected from hydrocarbyl in particular C1-12 alkyl, a group OR68 where R68 is hydrocarbyl in particular butyl, halogen in particular chlorine or a group R24-R28 where R24 and R28 are as defined in relation to formula (III) above, provided that at least two of R50 to R65 are R24-R28 groups, and R66 and R67 are either hydrogen or together comprise a metal ion such as a copper ion.
Preferably in formula (VIA), R51, R52, R55, R56, R59, R60, R63 and R64 are halogen and R50, R53, R54, R57, R58, R61, R62 and R65 are independently C1-12 alkyl, C1-12 alkoxy or a group R24-R28.
Polymerisation of a compound of formula (VI) or (VIA) in accordance with the scheme of FIG. 1, for example by photopolymerisation will provide a cross linked network polymer where the cross linking occurs through the diene units for example as either quaternery ammonium salts or amides depending upon the particular nature of the groups R1 and R6 present in the R21, R22, R23 and R24 units. Again this can produce a very stable network or elastomeric material with robust physical properties. In addition to conductivity, these polymers will be capable of exhibiting third order polarisabilities and they will be suitable for applications which employ the Kerr effect. These properties can be affected or moderated when metals or metal ions are inserted into the macrocyclic heterocyclic unit. Suitable metal ions include sodium, potassium, lithium, copper, zinc and iron ions.
Yet a further possibility for the bridging group R16 is a polysiloxane network polymer where R16 comprises a straight or branched siloxane chain of valency r or a cyclic polysiloxane unit.
Thus compounds of structure (VII) 
where R17, R18, R21 and R22 are as defined above in relation to formula (III), R28, R29, R30 are R31, are selected from hydrocarbyl such as alkyl and in particular methyl, and each R32 or R32 group is independently selected from hydrocarbyl or a group of formula R19-R23 where R19 and R23 are as defined above in relation to formula (III), and u is 0 or an integer of 1 or more, for example of from 1 to 20; and (VIII) 
where R17, R18, R19, R20, R21, R22, R23 and R24 are as defined above in relation to formula (III) and R28, R29, R30 and R31 are as defined above in relation to formula (VII), and r is 0 or an integer of 1 or more, for example from 1 to 5. In a particular embodiment, formula (VIII) has four siloxane units in the ring (i.e. r is 1). It will be appreciated that there may be other numbers of such units in the, cyclic ring, for example from 3 to 8 siloxane units (r is from 0 to 5), preferably from 3 to 6 siloxane units(r is from 0 to 3).
In the above structures (VII) and (VIII), it will be appreciated that xe2x80x94Sixe2x80x94 may be replaced by B or Bxe2x88x92; or xe2x80x94Sixe2x80x94Oxe2x80x94 is replaced by xe2x80x94Bxe2x80x94N(R40)xe2x80x94 where R40 is a hydrocarbyl group such as those defined above in relation to group R32 in formula (VII) or a group xe2x80x94R24-R28 as defined in relation to formula (VIII) above.
Upon polymerisation, compounds of formula (VII) and (VIII) or variants thereof, will form a cross-linked network where the cross-linking occurs through the groups R21, R22, R23 and R24 as illustrated in FIG. 1. Such polymers may exhibit properties similar to those of conventional siloxanes. However, in the case of compounds of formula (VII) and (VIII), they may be coated onto surfaces and polymerised in situ, for example using radiation curing.
Further examples of compounds of formula (I) include compounds of formula (IX) 
where R17, R18, R19, R20, R21, R22, R23 and R24 are as defined above in relation to formula (III).
Particular examples of compounds of formula (I) and related compounds are listed in Table 2 below:
Compounds of formula (I) are suitably prepared by conventional methods, for example by reacting a compound of formula (X) 
where X2, X3, Y2, Y3, R2, R3, R4 and R5 are as defined in relation to formula (I), R1, is a group R1 as defined in relation to formula (I) or a precursor thereof, R35 is hydrogen or hydroxy, with a compound of formula (XI)
R16xe2x80x94[R6xe2x80x94Z4]rxe2x80x83xe2x80x83(XI)
where R6, R16 and r are as defined in relation to formula (I) and Z4 is a leaving group, and thereafter if desired or necessary converting a precursor group R1xe2x80x2 to a group R1.
Suitable leaving groups Z4 include halogen, in particular bromo, mesylate or tosylate. The reaction is suitably effected in an organic solvent such as tetrahydrofuran, dichloromethane, toluene, an alcohol such as methanol or ethanol, or a ketone such as butanone and at elevated temperatures for example near the boiling point of the solvent.
Preferably the reaction is effected in the presence of a base such as potassium carbonate.
When the group R1xe2x80x2 is a precursor of the group R1, it may be converted to the corresponding R1 group using conventional techniques. For example R1xe2x80x2 may be a nitrogen atom, which may be converted to a group NR12(Zmxe2x88x92)1/m where R12, Z and m are as defined above, by reaction with an appropriate salt under conventional conditions. Examples of this are illustrated hereinafter.
Compounds of formulae (X) and (XI) are either known compounds or they can be prepared from known compounds by conventional methods.
Thus the invention further provides a method for producing a polymeric material, said method comprising causing a compound of formula (I) to polymerise. Suitably the compound of formula (I) is a radiation curable compound and polymerisation is effected by subjecting the compound to the appropriate radiation (e.g. heat or ultraviolet radiation) and if necessary in the presence of a suitable initiator such as a photoinitiator like AIBN. Where the compound of formula (I) cannot or it is not appropriate for it to be cured in this way, other conventional polymerisation techniques can be employed as would be understood in the art.
Radiation curing of compounds of formula (I) and related compounds form a further aspect of the invention. Thus the invention further provides a method of producing a polymer which comprises subjecting a compound of formula (IB) 
where
R1xe2x80x3 is CH and R6xe2x80x3 a bond, or R1xe2x80x3 and R6xe2x80x3 together form an electron withdrawing group;
R2xe2x80x3 and R3xe2x80x3 are independently selected from (CR7xe2x80x3R8xe2x80x3)nxe2x80x3, or a group CR9xe2x80x3R10xe2x80x3, xe2x80x94(CR7xe2x80x3R8xe2x80x3CR9xe2x80x3R10xe2x80x3)xe2x80x94 or xe2x80x94(CR9xe2x80x3R10xe2x80x3CR7xe2x80x3R8xe2x80x3)xe2x80x94 where nxe2x80x3 is 0, 1 or 2, R7xe2x80x3 and R8xe2x80x3 are independently selected from hydrogen or alkyl, and either one of R9xe2x80x3 or R10xe2x80x3 is hydrogen and the other is an electron withdrawing group, or R9xe2x80x3 and R10xe2x80x3 together form an electron withdrawing group, and
R4xe2x80x3 and R5xe2x80x3 are independently selected from CH or CR11xe2x80x3 where R11xe2x80x3 is an electron withdrawing group;
X1 and Y1xe2x80x3 are groups as defined for X1 and Y1 respectively in relation to formula (I;
R16xe2x80x3 is a bridging group of valency rxe2x80x3 and rxe2x80x3 is an integer of 2 or more,
provided that at least one of (a) R1xe2x80x3 and R6xe2x80x3 or (b) R2xe2x80x3 and R3xe2x80x3 or (c) R4xe2x80x3 and R5xe2x80x3 includes an electron withdrawing group, to radiation under conditions which would cause the compound of formula (Ib) to polymerise.
Preferred groups in the compounds of formula (Ib) are those described above in relation to the corresponding groups of the compound of formula (I).
During the polymerisation process, the compounds of formula (I) (IA) or (IB) link together by way of the unsaturated bonds such as the diene groups as illustrated in FIG. 1. Because the compounds of formula (I), (IA) and (IB) include at least two diene groups, they will tend to become cross linked to form a network or three dimensional structure. The degree of cross linking can be controlled by carrying out the polymerisation in the presence of cross-linkers, where for example r is greater than 2, for example 4, or diluents, plasticisers or chain terminators. These will suitably comprise a compound of formula (XII) 
where X1, X2, Y1, Y2, R1, R2, R3, R4, R5, R6, R16 and r are as defined in relation to formula (I). Compounds of formula (I) may be used in the preparation of homopolymers or copolymers where they are mixed with other monomeric units, which may themselves be of formula (I) or otherwise.
A general scheme illustrating the sort of polymerisation process which may occur using a polyethylene type bridging group is illustrated in FIG. 2.
Polymeric compounds obtained form a further aspect of the invention. Thus the invention further provides a polymeric compound of formula (XIII) 
where A is a bond or or CH2, R1, R2, R3, R4, R5, R6 are as defined in relation to formula (I), R16xe2x80x2 is a group of formula R16 as defined in formula (I) which may be substituted by further groups of sub formula (XIV) 
and y is an integer in excess of 1, preferably in excess of 5 and suitably from 5 to 30 and A is as defined above. It will be understood that copolymers also fall within the scope of this definition as outlined above.
Using the compounds of the invention, it is possible to take a suitable organic system that has optimal or optimised properties for use in certain applications, eg, high yield strength, large hyperpolarisability, high pyroelectric coefficient, high conductivity etc, and to structurally modify the system so that it is possible to polymerise it. If functional groups are incorporated that will polymerise, it will become possible to create a three dimensional network or plastic that will have properties associated with the parent organic system.
The advantages of the compounds of the invention is that they allow for the possibility that they can be applied in the form of a paint and caused to polymerise in situ. Thus this allows for ease of processing. Further, by providing for the construction of networks as a result of the cross linking, the resultant polymer can be mechanically strong and durable.
The versatility of the systems of the.invention mean that it is possible to build in anisotropy which would improve directional physical properties, eg NLO, mechanical yield strength etc.
Both amorphous or ordered systems can be prepared depending upon the particular polymerisation conditions used. Copolymerisation is also possible which can be used advantageously to affect physical properties of the polymer obtained.
Systems can be prepared which mimic conventional polymers/elastomers, or which involve donor/acceptor systems.
Polymers of the invention are particularly suitable for the production of adhesive coatings, and multilayer coatings as well as binders. It is possible to manipulate the low molar mass coating before polymerisation is carried out, eg, poling etc.
Films of polymeric material can be prepared as illustrated hereinafter. Thus material with the properties of for example, polyethylene films can be produced using radiation curing techniques if required.
Polymer coatings prepared as described herein have useful water-proofing, corrosion resistance and general dust and dirt protective properties, in particular where they include halogenated and particularly fluorinated bridging groups. Thus they may be used in the production of fabrics such as clothing, electrical components or devices, mechanical components as well as building materials which require this feature. In addition, coatings of this type may produce anti-icing features which are useful, particularly where these materials are exposed to harsh external conditions. Products treated in this way also exhibit strong pearling qualities and this assists in the rapid shedding of condensate. Thus surfaces remain relatively free of such condensates.
Such surfaces can be achieved on at least part of the internal surfaces of a structure containing interconnecting intersitial spaces, such as fibrous or granular material.
The present invention provides a product selected from a fabric, an electrical component or device, a mechanical component, or a construction or building material, having deposited thereon a polymeric coating derived from a monomer of formula (IA) as defined above.
Suitable electrical components include small electrical components such as resistors, capacitors, condensers, circuit breakers, switches and connectors, as well as small assemblies of these, for example circuit boards on which these and/or other components are mounted. Electrical devices include conductors, such as HT leads for example, those used in automobile engines, and cables such as external or underground power cables. Such cables may be pre-coated with plastics of another insulating material.
Plastics coatings in accordance with the invention may be applied to electrical wiring. In particular, monomers of formula (IA) or (IB) which mimic polypropylene would be useful in this context.
Mechanical components include housings, bearings, shafts, gears, wheels, gaskets, filter housing, engines, gearboxes, transmission, steering or suspension components.
Building materials include wood, brick, concrete slabs or other preformed concrete structures, building blocks, stone, slates or insulation materials where there is a possibility that corrosion, weathering or water penetration is likely to cause problems.
Polymer coatings formed in accordance with the invention may be useful in electronic components which have a polymeric coating as resistance layers. The nature of the bridging group R16 will affect the resistance of the polymer layer.
Optionally the bridging group R1 may be aromatic or heteroaromatic, i.e. it may include one or more unsaturated carbon rings, optionally containing heteroatoms such as nitrogen, oxygen or sulphur, which give the surface formed additional resistance to etching by plasma etch processes as used in the semiconductor integrated circuit industry.
If necessary, the coating may be discontinuous, for example, patterned by etching, optionally after masking certain areas, so as to provide the desired electronic properties. Techniques for achieving this are well known, and include for example, irradiation with high energy radiation such as electron beams, X-rays or deep ultraviolet rays.
The irradiation breaks the bonds in the polymer and exposed areas can then be dissolved in a developer liquid. Optionally, the coating may consist of a mixture of a monomer and a chemical designed to enhance its sensitivity to radiation exposure during the patterning process, such as quinione diazide or anthraquinone.
Suitable electronic components include printed circuit boards, semiconductor elements, optical devices, videodiscs, compact discs, floppy discs and the like.